US10725215B2 - Optical filter and imaging device comprising same - Google Patents

Optical filter and imaging device comprising same Download PDF

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US10725215B2
US10725215B2 US15/558,865 US201615558865A US10725215B2 US 10725215 B2 US10725215 B2 US 10725215B2 US 201615558865 A US201615558865 A US 201615558865A US 10725215 B2 US10725215 B2 US 10725215B2
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zone
binder resin
resin matrix
light absorbent
zones
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US20180074241A1 (en
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Jin Ho Jung
Joo Young Kim
Youn Ha HWANG
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LMS Co Ltd
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LMS Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • the present invention relates to an optical filter and an imaging device including the same.
  • Image signals of the digital camera modules are received through an image sensor.
  • An image sensor composed of semiconductors has a characteristic of responding even to wavelengths in an infrared (IR) region, unlike human eyes. Therefore, an IR filter configured to block the wavelengths in the IR region is required to obtain information on images similar to those observed by the human eyes.
  • IR infrared
  • the IR filter When such an IR filter has a low pixel count of two million pixels or less, the IR filter generally has a combined structure of an anti-reflective coating layer (AR coating layer) and an infrared reflective coating layer (IR coating layer), both of which are obtained by repeatedly stacking a metal oxide on both sides of a glass material.
  • AR coating layer anti-reflective coating layer
  • IR coating layer infrared reflective coating layer
  • the AR coating layer and the IR coating layer obtained by repeatedly stacking the metal oxide have characteristics such as a big change in spectroscopic properties according to an angle of incidence of light.
  • the digital camera modules have continued to develop toward an increase in pixels of the image sensor. In such a structure with high pixels, a change in spectroscopic properties according to an angle increases, resulting in degraded quality of images.
  • a structure of a high-pixel digital camera equipped with an IR filter including an infrared absorbent has been used.
  • an AR coating layer and a near-infrared reflective coating layer are formed by depositing a metal oxide and the like on one or both surfaces of a binder resin matrix in which a light absorbent is dispersed.
  • NIR coating layer a near-infrared reflective coating layer
  • conventional film-type infrared absorption filters have a structure in which an absorbent is dispersed throughout the film.
  • Such a structure has problems in that it causes haze that reduces image quality of a photographed image, and it is difficult to maintain high transmittance with respect to wavelengths in a visible region required for high-pixel digital cameras.
  • Patent Document 1 US Patent Publication No. 2013-0094075
  • the present invention is directed to providing a film-type optical filter capable of effectively cutting off infrared rays (an IR cut off effect), and an imaging device including the same.
  • One aspect of the present invention provides an optical filter which includes:
  • binder resin matrix in which the light absorbent is dispersed is composed of a single layer
  • the binder resin matrix includes n zones (where n is an integer ranging from 3 to 7) equally divided in a thickness direction of the matrix, and
  • Another aspect of the present invention provides an imaging device including the optical filter according to the present invention.
  • Still another aspect of the present invention provides a method of manufacturing an optical filter according to the present invention, which includes:
  • the thermally treating of the binder resin matrix coated with the solution in which the light absorbent is dispersed is performed at a temperature of 130 to 150° C.
  • FIG. 1 is a cross-sectional view showing a stacked structure of a conventional optical filter
  • FIGS. 2 to 4 are cross-sectional views showing stacked structures of optical filters according to one exemplary embodiment of the present invention, respectively;
  • FIGS. 5 to 14 are graphs illustrating results of measuring degrees of warpage of polymer resin matrices according to one exemplary embodiment of the present invention, respectively.
  • FIGS. 15 and 16 are graphs illustrating results of measuring light transmittance spectra of optical filters according to one exemplary embodiment of the present invention, respectively, to compare the light transmittance spectra of the optical filters.
  • first means “first,” “second,” etc.
  • these elements are not limited by these terms. These terms are only used to distinguish one element from another. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of exemplary embodiments.
  • the term “and/or” includes any and all combinations of one or more of the associated listed items.
  • an optical filter which includes:
  • binder resin matrix in which the light absorbent is dispersed is composed of a single layer
  • the binder resin matrix includes n zones (where n is an integer ranging from 3 to 7) equally divided in a thickness direction of the matrix, and
  • the optical filter has a structure in which a light absorbent is dispersed in a portion of each of zones divided in a thickness direction of the binder resin matrix. Such a structure is configured to contrast with the conventional structure in which the light absorbent is dispersed through the binder resin matrix.
  • the optical filter according to the present invention also has a structure in which the light absorbent is dispersed in a portion of the binder resin matrix. Therefore, it is possible to fundamentally prevent the occurrence of defects or delamination at the interface between a resin layer and light absorption layer. This is different from the configuration in which a separate light absorption layer is formed on one or both surfaces of the resin layer.
  • the binder resin matrix according to the present invention may be divided into three or more zones in a thickness direction.
  • the expression “binder resin matrix being divided into zones in a thickness direction” means that the zones may be recognized to be distinguished depending on the concentration of the light absorbent dispersed in the zones, but does not mean that layers are physically distinguishable.
  • At least one zone may be a zone in which the light absorbent is dispersed at a relatively high concentration, and a zone in which the light absorbent is dispersed at a relatively low concentration.
  • an amount of the light absorbent may be greater than or equal to 40% or 70%, or may be in a range of 40 to 99%, 70 to 99%, 40 to 50%, 60 to 95%, or 80 to 99%, based on the total amount (A) of the light absorbent.
  • the binder resin matrix includes both the zone in which the light absorbent is dispersed at a high concentration and the zone in which the light absorbent is dispersed at a low concentration, warpage caused in a manufacturing process may be suppressed.
  • the zone in which the light absorbent is dispersed at a high concentration and the zone in which the light absorbent is dispersed at a low concentration have different stress values.
  • the stress may be regulated by adjusting a concentration of the dispersed light absorbent, and warpage may be effectively prevented by combining zones having different stress values.
  • a degree of freedom of design in manufacturing of the optical filter may be enhanced. That is, even when an oxide is deposited on one or both surfaces of the binder resin matrix, the oxide may be deposited to have various compositions and thicknesses by adjusting the concentration of the dispersed light absorbent and combining the zones having different stress values.
  • haze may be reduced through this configuration.
  • Image qualities and resolutions of images photographed with a digital camera may be reduced as the haze of the optical filter increases.
  • the image qualities and resolutions of the images are greatly influenced by the haze as the pixel size of the image sensor decreases. Therefore, degradation of image qualities and resolutions of images and videos may be prevented by reducing the haze of the optical filter in the high-pixel digital camera.
  • the optical filter may have a haze value of 0.2% or less, 0.1% or less, or 0.07% or less.
  • Types of the binder resin used to form the binder resin matrix are not particularly limited.
  • one or more compounds selected from the group consisting of various types of dyes, pigments or metal complex compounds may be used as the light absorbent, but the present invention is not particularly limited thereto.
  • a cyanine-based compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, or a dithiol metal complex compound may be used as the light absorbent.
  • the light absorbents may be used alone, and may be used in combination of two or more types thereof, when necessary.
  • the binder resin matrix includes a first zone, a k th zone (where k is an integer ranging from 2 to n-1), and an n th zone (where n is an integer ranging from 3 to 7) when one surface of the matrix is divided into zones in a thickness direction, and
  • At least one of the first zone and the n th zone may be a zone in which 40% or more of the light absorbent is dispersed based on the total amount of the light absorbent.
  • the binder resin matrix includes a first zone, a k th zone (where k is an integer ranging from 2 to n-1), and an n th zone (where n is an integer ranging from 3 to 7) when one surface of the matrix is divided into zones in a thickness direction, and the first zone or the n th zone may be a zone in which 70% or more, 80% or more, 90% or more, or 70 to 99% of the light absorbent is dispersed based on the total amount of the light absorbent.
  • the binder resin matrix includes a first zone, a k th zone (where k is an integer ranging from 2 to n-1), and an n th zone (where n is an integer ranging from 3 to 7) when one surface of the matrix is divided into zones in a thickness direction, at least one of the first zone and the n th zone may be a zone in which 10% or less of the light absorbent is dispersed based on the total amount of the light absorbent, and the k th zone may be a zone in which 40% or more of the light absorbent is dispersed based on the total amount of the light absorbent.
  • an optical filter may be prepared, for example, by coating a surface of the binder resin matrix with a solution including the light absorbent, thermally treating the binder resin matrix to remove the solvent, and again coating the surface of the binder resin matrix with a solution including no light absorbent.
  • the binder resin matrix includes five zones into which one surface of the matrix is divided in a thickness direction, and at least one of the first zone and the fifth zone may be a zone in which 10% or less, 5% or less, 1% or less, or 10 to 0.001% of the light absorbent is dispersed based on the total amount of the light absorbent. Also, at least one of the first zone and the fifth zone may be a zone in which 40% or more of the light absorbent is dispersed based on the total amount of the light absorbent.
  • the binder resin matrix according to the present invention has a significantly lowered degree of warpage.
  • the binder resin matrix in which the light absorbent is dispersed satisfies the following Expression 1.
  • F max refers to a warpage value of a specimen
  • F max for a specimen having a size of 10 mm ⁇ 10 mm (width ⁇ length), represents the maximum separation distance from a straight line connecting both ends of a specimen in a ⁇ 2.3 mm section in a horizontal direction (X axis) with respect to the center of the specimen.
  • the F max value disclosed in Expression 1 may be less than or equal to 40 ⁇ m, 35 ⁇ m, or 15 ⁇ m, or in a range of 0.5 to 40 ⁇ m, 10 to 40 ⁇ m, or 1 to 15 ⁇ m.
  • a degree of occurrence of warpage may be remarkably lowered by dispersing a varying concentration of the light absorbent in the binder resin matrix in a thickness direction.
  • the occurrence of warpage may be suppressed to the maximum extent. When necessary, the warpage may be induced in one direction.
  • a film When the occurrence of warpage of the binder resin matrix is suppressed, a film may have high flatness, and it is desirable to manufacture an optical filter whose surface is close to being horizontal. Also, when the occurrence of warpage of the binder resin matrix is induced, the degrees of warpage caused during deposition of an additionally stacked metal oxide may be summed up to manufacture an optical filter in a desired shape. In this way, a degree of freedom of design for the optical filter may be enhanced.
  • the optical filter according to one exemplary embodiment of the present invention may include a near-infrared reflective coating layer (an NIR coating layer) formed on one or both surfaces of the binder resin matrix in which the light absorbent is dispersed.
  • the optical filter according to one exemplary embodiment of the present invention may include both an NIR coating layer formed on a first surface of the binder resin matrix in which the light absorbent is dispersed, and an anti-reflective coating layer (AR coating layer) formed on a second surface of the binder resin matrix in which the light absorbent is dispersed.
  • an NIR coating layer formed on a first surface of the binder resin matrix in which the light absorbent is dispersed
  • AR coating layer anti-reflective coating layer
  • the NIR coating layer may be formed as a multilayer dielectric film.
  • the NIR coating layer serves to reflect light of a near-infrared region.
  • a multilayer dielectric film in which a high refractive index layer and a low refractive index layer are alternately stacked may be used as the NIR coating layer.
  • the NIR coating layer may further include an aluminum-deposited film, a noble metal thin film, or a resin film in which fine particles of either indium oxide or tin oxide are dispersed.
  • the NIR coating layer may have a structure in which a dielectric layer having a first refractive index and a dielectric layer having a second refractive index are alternately stacked.
  • a difference in refractive index between the dielectric layer having a first refractive index and the dielectric layer having a second refractive index may be greater than or equal to 0.2, or 0.3, or in a range of 0.2 to 1.0.
  • the dielectric layer having a first refractive index may be a layer having a relatively high refractive index
  • the dielectric layer having a second refractive index may be a layer having a relatively low refractive index.
  • the refractive index of the dielectric layer having a first refractive index may be in a range of 1.6 to 2.4
  • the refractive index of the dielectric layer having a second refractive index may be in a range of 1.3 to 1.6.
  • the dielectric layer having a first refractive index may be formed of at least one selected from the group consisting of titanium oxide, alumina, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, and indium oxide.
  • the indium oxide may further include a small amount of titanium oxide, tin oxide, or cerium oxide, when necessary.
  • the dielectric layer having a second refractive index may be formed of at least one selected from the group consisting of silica, lanthanum fluoride, magnesium fluoride, and sodium fluoride alumina.
  • a method of forming the NIR coating layer is not particularly limited, and the NIR coating layer may, for example, be formed using a method such as CVD, sputtering, vacuum deposition, etc.
  • the NIR coating layer may have a structure in which the dielectric layer having a first refractive index and the dielectric layer having a second refractive index are alternately stacked 5 to 61 times, 11 to 51 times, or 21 to 41 times.
  • the NIR coating layer may be designed in consideration of a desired range of transmittance and refractive index, a region of wavelengths to be blocked, etc.
  • the NIR coating layer may further include a light absorbent dispersed in the multilayer dielectric film.
  • the light absorbent dispersed in the multilayer dielectric film may be used without any particular limitation as long as the light absorbent can absorb light in a near-infrared (500 nm or more) to infrared wavelength region.
  • the light absorbent may be dispersed in the multilayer dielectric film to reduce the number of alternately stacked layers in the multilayer dielectric film, thereby reducing a thickness of the NIR coating layer. In this way, when the NIR coating layer is applied to imaging devices, the imaging devices may be made smaller.
  • the multilayer dielectric film having a smaller thickness may be manufactured. In this way, the imaging devices may be made smaller.
  • the AR coating layer serves to reduce a phenomenon in which light incident on the optical filter is reflected at the interface. In this way, a quantity of light incident on the optical filter increases.
  • the AR coating layer is formed to reduce surface reflectivity to enhance reflection efficiency and remove interference and scattering caused by reflected light.
  • the AR coating layer may be formed by forming a film on a surface of a dielectric material having a lower refractive index than glass using methods such as vacuum deposition, etc.
  • films may be formed using various commercially available materials without particular limitation.
  • the present invention provides an imaging device including the aforementioned optical filter.
  • the imaging device includes a camera device installed in a mobile device such as a mobile phone, a camera device installed in a digital camera and a laptop computer, a camera device for CCTV, etc., but the present invention is not particularly limited thereto.
  • the present invention provides a method of manufacturing the aforementioned optical filter.
  • the method of manufacturing an optical filter may include coating one or both surfaces of a light-transmitting film with a solution in which a light absorbent is dispersed, and thermally treating the coated binder resin matrix.
  • various processes for the method such as slot-die coating, microgravure coating, spin coating, and solution casting, may be used as the process of applying the light absorbent.
  • the thermally treating of the binder resin matrix may be performed at a temperature of 130 to 150° C.
  • the light absorbent may penetrate into the binder resin matrix so that the light absorbent can be partially dispersed in the binder resin matrix.
  • the method of manufacturing an optical filter may also include a method of partially injecting a solution including the light absorbent into the binder resin matrix.
  • FIG. 1 is a cross-sectional view showing a stacked structure of a conventional optical filter according to the present invention.
  • the conventional optical filter includes a light absorbent 11 dispersed throughout a binder resin matrix 10 .
  • the conventional optical filter is configured so that an AR coating layer 20 is formed on one surface of the binder resin matrix 10 , and an NIR coating layer 30 is formed on the opposite surface of the binder resin matrix 10 . Because the optical filter shown in FIG. 1 has a structure in which the light absorbent 11 is dispersed throughout the binder resin matrix 10 , an increase in amount of the light absorbent 11 used herein may be inevitably caused.
  • the light absorbent 11 dispersed in the binder resin matrix 10 may serve as impurities in terms of light transmittance and thus haze is caused. Also, because the optical filter shown in FIG. 1 has a relatively simple stacked structure, warpage may be induced due to the stress caused during formation of the AR coating layer 20 and the NIR coating layer 30 .
  • FIGS. 2 to 4 are cross-sectional views showing stacked structures of optical filters according to one exemplary embodiment of the present invention, respectively.
  • a high concentration of a light absorbent 110 is dispersed in a first zone 101 disposed at an upper inner portion of a binder resin matrix 100 .
  • An AR coating layer 200 is formed on one surface of the binder resin matrix 100
  • an NIR coating layer 300 is formed on the opposite surface of the binder resin matrix 100 .
  • the optical filter shown in FIG. 2 has a structure in which the light absorbent 110 is intensively dispersed in the first zone 101 of the binder resin matrix 100 . As a result, it is possible to reduce an amount of the light absorbent 110 used and manufacture thin optical filters, resulting in reduced haze.
  • a degree of dispersion of the light absorbent 110 may be controlled to induce occurrence of stress with respect to the binder resin matrix 100 in one direction.
  • the optical filter may be designed so that stress caused due to intensive dispersion of the light absorbent 110 and stress caused during stacking of an AR coating layer 200 and an NIR coating layer 300 to be stacked below act in opposite directions. In this way, it is possible to manufacture a film-type optical filter whose warpage is significantly reduced.
  • a high concentration of the light absorbent 110 is dispersed in a second zone 102 disposed at a lower inner portion of a binder resin matrix 100 .
  • a high concentration of the light absorbent 110 is dispersed in both of the first zone 101 and second zone 102 of the binder resin matrix 100 .
  • At least one of the AR coating layer 200 and the NIR coating layer 300 may be omitted, when necessary. Also, a structure in which the AR coating layer 200 and the NIR coating layer 300 are sequentially stacked on the same plane with respect to the binder resin matrix 100 is not excluded.
  • optical filter having a novel structure according to the present invention will be described in detail with reference to specific embodiments of the present invention.
  • the following examples are just preferred examples for the purpose of illustration only and are not intended to limit or define the scope of the present invention.
  • a light absorbent which was commercially available and has a maximum absorption of 690 nm was mixed with toluene (commercially available from Sigma Aldrich), and the resulting mixture was stirred for 24 hours or more to prepare a solution for near-infrared absorption.
  • a depth of penetration of a light absorbent into the binder resin matrix was adjusted by controlling a concentration of the solution for near-infrared absorption.
  • the concentration of the solutions for near-infrared absorption prepared in Examples 1 to 5 were adjusted so that average depths of penetration of the light absorbent into the binder resin matrix were adjusted to be 8 ⁇ m, 17 ⁇ m, 26 ⁇ m, 35 ⁇ m, and 44 ⁇ m, respectively.
  • TiO 2 and SiO 2 were alternately deposited on one surface of the binder resin matrix, into which the light absorbent penetrated, using an E-beam evaporator to form an NIR coating layer having a thickness of 5.5 ⁇ m. Thereafter, TiO 2 and SiO 2 were alternately deposited on a surface of the binder resin matrix opposite to the surface on which the NIR coating layer was formed to form an AR coating layer having a thickness of 3.2 ⁇ m.
  • the manufactured optical filter was measured to have a total thickness of 108.7 ⁇ m.
  • Optical filters were manufactured in the same manner as in Example 1, except that both surfaces of the binder resin matrix were coated with the prepared solution for near-infrared absorption, and the solvent was then evaporated.
  • the concentration of the solutions for near-infrared absorptions prepared in Examples 6 to 10 were adjusted so that average depths of penetration of the light absorbent into the binder resin matrix were adjusted to be 8 ⁇ m, 17 ⁇ m, 26 ⁇ m, 35 ⁇ m, and 44 ⁇ m, respectively.
  • a light absorbent which was commercially available and has a maximum absorption of 690 nm was mixed with toluene (commercially available from Sigma Aldrich), and the resulting mixture was stirred for 24 hours or more. Thereafter, the stirred solution was solution-cast, and then cured so that the light absorbent was uniformly distributed in a binder resin matrix.
  • TiO 2 and SiO 2 were alternately deposited on one surface of the binder resin matrix, with which the light absorbent was mixed, using an E-beam evaporator to form an NIR coating layer having a thickness of 5.5 ⁇ m. Thereafter, TiO 2 and SiO 2 were alternately deposited on a surface of the binder resin matrix opposite to the surface on which the NIR coating layer was formed to form an AR coating layer having a thickness of 3.2 ⁇ m.
  • a light absorbent which was commercially available and has a maximum absorption of 690 nm was mixed with toluene (commercially available from Sigma Aldrich), and the resulting mixture was stirred for 24 hours or more to prepare a solution for near-infrared absorption.
  • One surface of a binder resin matrix was coated with the prepared solution for near-infrared absorption, and the solvent was then evaporated through thermal treatment.
  • a surface of the binder resin matrix from which the solvent was completely evaporated was coated with a toluene solution including no light absorbent to prepare an optical filter so that the light absorbent was disposed in a portion of an inner zone of the binder resin matrix.
  • a depth of penetration of the light absorbent into the binder resin matrix was controlled to an average depth of 26 ⁇ m, and a zone in which the light absorbent was not dispersed up to 8 ⁇ m from a surface of the binder resin matrix was formed.
  • TiO 2 and SiO 2 were alternately deposited on one surface of the binder resin matrix, into which the light absorbent penetrated, using an E-beam evaporator to form an NIR coating layer having a thickness of 5.5 ⁇ m. Thereafter, TiO 2 and SiO 2 were alternately deposited on a surface of the binder resin matrix opposite to the surface on which the NIR coating layer was formed to form an AR coating layer having a thickness of 3.2 ⁇ m.
  • the manufactured optical filter was measured to have a total thickness of 108.7 ⁇ m.
  • a degree of warpage of each of the light absorbents prepared in Examples 1 to 10 in which a light absorbent was dispersed was measured.
  • UA3P commercially available from Panasonic Corp. was used to perform the measurements to calculate a degree of warpage.
  • a specimen used to measure a degree of warpage was cut into pieces having a size of 10 mm ⁇ 10 mm (width ⁇ length). Thereafter, a degree of warpage of a ⁇ 2.3 mm section in a horizontal direction (X axis) with respect to the center of the specimen was calculated. The degree of warpage was measured as a separation distance from a straight line connecting both ends of the specimen. Here, both ends of the specimen represent points at ⁇ 2.3 mm. The degrees of warpage were calculated at the respective points. Among these, the maximum value was selected as a warpage value.
  • the degrees of warpage of the polymer resin matrices were in a range of 2.2 to 12.2 ⁇ m in the case of Examples 6 to 10 in which the light absorbent penetrated into both sides of each of the polymer resin matrices.
  • the warpage of the polymer resin matrices was remarkably reduced, compared to those of Examples 1 to 5. From these facts, it was judged that the occurrence of warpage may be further minimized by forming layers, into which the light absorbent penetrated, on both surface of each of the polymer resin matrices.
  • FIG. 15 shows results of measuring light transmittance spectra of the optical filters of Example 1 (B) and Comparative Example 1 (A) to compare the light transmittance spectra of the optical filters.
  • FIG. 16 shows results of measuring light transmittance spectra of the optical filters of Example 6 (C) and Comparative Example 1 (A) to compare the light transmittance spectra of the optical filters.
  • Example 1 Example 6
  • Example 1 Average 87.74% 87.87% 87.05% transmittance Minimum 79.86% 79.96% 74.98% transmittance T50% 643.2 nm 643.8 nm 643.7 nm
  • the average transmittance is a value obtained by calculating an average value of light transmittance in a wavelength region of 410 to 565 nm
  • the minimum transmittance is a value obtained by calculating the minimum value of the light transmittance in a wavelength region of 410 to 565 nm.
  • T50% represents the first wavelength value at which the light transmittance reaches 50% in a wavelength region of 600 nm or more.
  • the optical filters manufactured in Examples 1 and 6 had an average light transmittance of 87.5% or more and the minimum transmittance of 79% or more in a wavelength region of 410 to 565 nm.
  • Example 1 Haze of each of the optical filters manufactured in Example 1 and Comparative Example 1 was measured.
  • the haze measurement was performed using NDH 2000N commercially available from Nippon Denshoku Industries Co., Ltd.
  • Example 3 it was revealed that the optical filter manufactured in Example 1 had an average haze value of 0.06%, but the optical filter manufactured in Comparative Example 1 had an average haze value of 0.31%. From these facts, it can be seen that the haze of the optical filter according to the present invention was significantly reduced to approximately 20% of that of the conventional optical filter.
  • the haze value measured in Experimental Example 3 is preferably less than or equal to 0.2%, and more preferably less than or equal to 0.1%.

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KR102491491B1 (ko) 2017-09-08 2023-01-20 삼성전자주식회사 근적외선 흡수 필름용 조성물, 근적외선 흡수 필름, 카메라 모듈 및 전자 장치
KR102125390B1 (ko) 2019-01-30 2020-06-22 한국과학기술원 유리 클로스 투명 복합체를 포함하는 흡수형 광학 필터 및 그 제조방법

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US20180074241A1 (en) 2018-03-15
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KR20160111877A (ko) 2016-09-27
CN107430226A (zh) 2017-12-01

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